CA2842704C - Amphiphilic macromolecule and use thereof - Google Patents
Amphiphilic macromolecule and use thereof Download PDFInfo
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- CA2842704C CA2842704C CA2842704A CA2842704A CA2842704C CA 2842704 C CA2842704 C CA 2842704C CA 2842704 A CA2842704 A CA 2842704A CA 2842704 A CA2842704 A CA 2842704A CA 2842704 C CA2842704 C CA 2842704C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/06—Clay-free compositions
- C09K8/12—Clay-free compositions containing synthetic organic macromolecular compounds or their precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Treatment Of Sludge (AREA)
Abstract
The present invention provides an amphiphilic macromolecule and the use thereof. The amphiphilic macromolecules have repeating structural units: structural units to adjust molecular weight and molecular weight distribution and charging property effects, high stereo-hindrance structural units, and amphiphilic structural units, and are suitable for fields such as oil field well drilling, well cementation, fracturing, oil gathering and transfer, sewage treatment, sludge treatment and papermaking, etc., and can be used as an oil-displacing agent for enhanced oil production, a heavy oil viscosity reducer, a fracturing fluid, a clay stabilizing agent, a sewage treatment agent, a papermaking retention and drainage aid or a reinforcing agent, etc.
Description
International Application Number: PCT/CN2011/001579 Amphiphilic macromolecule and use thereof Technical Field This invention relates to an amphiphilic macromolecule and uses thereof, and this amphiphilic macromolecule is applicable to oilfield drilling, well cementing, fracturing, crude oil gathering and transporting, sewage treating, sludge treating and papermaking, and it can be used as intensified oil producing agent and oil displacing agent, heavy oil viscosity reducer, fracturing fluid, clay stabilizer, sewage treating agent, retention aid and drainage aid and strengthening agent for papermaking.
Background of the Invention Chemical flooding is one of the most effective and potential chemical technology for Enhanced Oil Recovery, which is especially represented by polymer flooding.
However, there arise some problems for conventional polymers along with the deep implementation of polymer flooding technology. Under reservoir conditions of high temperature and high salinity, the viscosifying capacity and thermal stability of the widely used polymer, partially hydrolyzed polyacrylamide (HPAM), reduces rapidly;
in the meantime, HPAM does not have the surface/interfacial activity per se, and could not start the oil film effectively, so that its ability to mine the remaining oil is limited. The polymer-based binary-component composite system (polymer/surfactant) and triple-component system (polymer/surfactant/alkali) may enhance the stability of the emulsified produced fluid, resulting in increased difficulty in oil/water separation and sewage treatment, as well as the weakening of synergistic effect among the components of the system under reservoir conditions, and also it may damage the reservoir. The application of the composite system is thus restricted.
It has become a difficulty and key for many large oilfield development to keep the viscosifying capacity and viscosity stability of the polymer solution, so as to achieve the strategic target of stabilization of oil production and water cut control.
Heavy oil is a collective name for unconventional oil, including heavy oil, high viscosity oil, oil sand, natural asphalt and etc., and they are also referred to as heavy International Application Number: PCT/CN2011/001579 oil, ultra-heavy oil, asphalt and etc. Among the approximate 10 trillion barrels of remaining oil resources around the world, more than 70% of which is heavy oil resource. Chinese onshore heavy oil and bitumen resources account for about more than 20% of their total oil resources. According to an incomplete statistics, the proved and controlled heavy oil reserves in China reach 1600 million tons. Nowadays heavy oil resource has become one of the important strategic replacement resources in China;
however, the exploitation of heavy oil is rather difficult. Chemical emulsification and viscosity reduction method has become an important exploitation technology.
Polymeric emulsification viscosity reducer usually refers to the polymeric surfactant with a relative molecular weight more than several thousands and significant surface activity; according to the ion types, it can be divided into four categories: anionic, cationic, zwitterionic and non-ionic polymeric surfactant.
Polymeric surfactant usually has limited capacity to reduce surface tension and oil-water interfacial tension, but has excellent emulsification and dispersion capability for heavy oil, with advantages of small usage amount, high viscosity reduction rate, lower cost and simple implementation process. In recent years, this research especially attracts more and more attention in this field.
Brief Description of the Invention In the following context of this invention, unless otherwise defined, the same variable group, and molecular and structural formula have the same definitions.
The instant invention relates to an amphiphilic macromolecule, this amphiphilic macromolecule has repeating units as described below: a structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics, a highly sterically hindered structural unit B and an amphiphilic structural unit C.
In an embodiment, the structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics comprises (meth)acrylamide monomer unit A1 and/or (meth)acrylic monomer unit A2. Preferably, the structural unit A includes (meth)acrylamide monomer unit A1 and / or (meth)acrylic monomer unit A2 simultaneously. In the art, the molecular weight of the amphiphilic
Background of the Invention Chemical flooding is one of the most effective and potential chemical technology for Enhanced Oil Recovery, which is especially represented by polymer flooding.
However, there arise some problems for conventional polymers along with the deep implementation of polymer flooding technology. Under reservoir conditions of high temperature and high salinity, the viscosifying capacity and thermal stability of the widely used polymer, partially hydrolyzed polyacrylamide (HPAM), reduces rapidly;
in the meantime, HPAM does not have the surface/interfacial activity per se, and could not start the oil film effectively, so that its ability to mine the remaining oil is limited. The polymer-based binary-component composite system (polymer/surfactant) and triple-component system (polymer/surfactant/alkali) may enhance the stability of the emulsified produced fluid, resulting in increased difficulty in oil/water separation and sewage treatment, as well as the weakening of synergistic effect among the components of the system under reservoir conditions, and also it may damage the reservoir. The application of the composite system is thus restricted.
It has become a difficulty and key for many large oilfield development to keep the viscosifying capacity and viscosity stability of the polymer solution, so as to achieve the strategic target of stabilization of oil production and water cut control.
Heavy oil is a collective name for unconventional oil, including heavy oil, high viscosity oil, oil sand, natural asphalt and etc., and they are also referred to as heavy International Application Number: PCT/CN2011/001579 oil, ultra-heavy oil, asphalt and etc. Among the approximate 10 trillion barrels of remaining oil resources around the world, more than 70% of which is heavy oil resource. Chinese onshore heavy oil and bitumen resources account for about more than 20% of their total oil resources. According to an incomplete statistics, the proved and controlled heavy oil reserves in China reach 1600 million tons. Nowadays heavy oil resource has become one of the important strategic replacement resources in China;
however, the exploitation of heavy oil is rather difficult. Chemical emulsification and viscosity reduction method has become an important exploitation technology.
Polymeric emulsification viscosity reducer usually refers to the polymeric surfactant with a relative molecular weight more than several thousands and significant surface activity; according to the ion types, it can be divided into four categories: anionic, cationic, zwitterionic and non-ionic polymeric surfactant.
Polymeric surfactant usually has limited capacity to reduce surface tension and oil-water interfacial tension, but has excellent emulsification and dispersion capability for heavy oil, with advantages of small usage amount, high viscosity reduction rate, lower cost and simple implementation process. In recent years, this research especially attracts more and more attention in this field.
Brief Description of the Invention In the following context of this invention, unless otherwise defined, the same variable group, and molecular and structural formula have the same definitions.
The instant invention relates to an amphiphilic macromolecule, this amphiphilic macromolecule has repeating units as described below: a structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics, a highly sterically hindered structural unit B and an amphiphilic structural unit C.
In an embodiment, the structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics comprises (meth)acrylamide monomer unit A1 and/or (meth)acrylic monomer unit A2. Preferably, the structural unit A includes (meth)acrylamide monomer unit A1 and / or (meth)acrylic monomer unit A2 simultaneously. In the art, the molecular weight of the amphiphilic
2 , International Application Number: PCT/CN2011/001579 .. , .
macromolecule may be selected as needed, preferably, this molecular weight may be selected between 1000000-20000000.
Preferably, the (meth)acrylamide monomer unit Al has a structure of formula (1):
--(- I
C H2 --C ----\-,--C---z---- 0 I
N
/ \ R
formula (1) In formula (1), R1 is H or a methyl group; R2 and R3 are independently selected from the group consisting of H and a C1-C3 alkyl group; R2 and R3 are preferably H.
Preferably, the (meth)acrylic monomer unit A2 is (meth)acrylic acid and/or (meth)acrylate. Preferably the (meth)acrylate is sodium methacrylate.
Preferably, the molar percentage of (meth)acrylamide monomer unit A1 in the whole amphiphilic polymer repeat units is 70-99mo1%; preferably 70-90mol%, more preferably 70-80mol%.
Preferably, the molar percentage of (meth)acrylic monomer unit A2 in the whole amphiphilic polymer repeat units is 1-30mol%; preferably 1-28mol%, more preferably 20-28mo1%.
In another embodiment, the structural unit A for the regulation of molecular weight, molecular weight distribution and charge characteristics has a structure of formula (2):
iC H2 ¨21-----(- C H2 -- C -- I
I
C=z----0 C -7------ 0 I
N Grl / \
i R3 Formula (2)
macromolecule may be selected as needed, preferably, this molecular weight may be selected between 1000000-20000000.
Preferably, the (meth)acrylamide monomer unit Al has a structure of formula (1):
--(- I
C H2 --C ----\-,--C---z---- 0 I
N
/ \ R
formula (1) In formula (1), R1 is H or a methyl group; R2 and R3 are independently selected from the group consisting of H and a C1-C3 alkyl group; R2 and R3 are preferably H.
Preferably, the (meth)acrylic monomer unit A2 is (meth)acrylic acid and/or (meth)acrylate. Preferably the (meth)acrylate is sodium methacrylate.
Preferably, the molar percentage of (meth)acrylamide monomer unit A1 in the whole amphiphilic polymer repeat units is 70-99mo1%; preferably 70-90mol%, more preferably 70-80mol%.
Preferably, the molar percentage of (meth)acrylic monomer unit A2 in the whole amphiphilic polymer repeat units is 1-30mol%; preferably 1-28mol%, more preferably 20-28mo1%.
In another embodiment, the structural unit A for the regulation of molecular weight, molecular weight distribution and charge characteristics has a structure of formula (2):
iC H2 ¨21-----(- C H2 -- C -- I
I
C=z----0 C -7------ 0 I
N Grl / \
i R3 Formula (2)
3 , International Application Number: PCT/CN2011/001579 wherein, R1 is H or a methyl group; R2 and R3 are independently selected from the group consisting of H and a C1-C3 alkyl group; R2 and R3 are preferably H;
R4 is selected from H or a methyl group; Gr is -OH or -0-Na ; m and n represent the molar percentage of the structural units among the entire amphiphilic macromolecule repeating unit, and m is 70-99mo1%, preferably 70-90mol%, more preferably 70-mol%; n is 1-30mol%, preferably 2-28mo1%, more preferably 20-28mol%.
In another embodiment, in formula (2), R1-R3 is preferably H, Gr is preferably -0-Na .
In another embodiment, the highly sterically hindered structural unit B
contains at least a structure Q wherein the structure G is a cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain, or is selected from a structure of formula (3), and the highly sterically hindered structural unit B
optionally contains a structure of formula (4):
R
I
CH2-C --)---(- CH2 - C 1---0 = C
I
\\:......,,z,...\,, formula (3) formula (4) In formula (3), R5 is H or a methyl group; preferably H; R6 is a radical selected from the group consisting of the structures of formulas (5) and (6).
/CH2 -0(CH2).CH, / \
CH2 - 0(CH2)2COOCH2CH3 CH2 -0(CH2).CH3 \ /
CH2 - 0(CH2).CH3 ¨ NH ¨C -- CH2¨ 0(CH2)2COOCH2CH3 cH2 - 0 -CH
\ \
CH2 - 0(CH2).CH3 CH, - 0(CH2)2COOCH2CH3 formula (5) , and formula (6) In formula (5), a is an integer from 1 to 11; preferably 1-7;
In formula (4), R7 is H; R8 is selected from H, -S03H and salts thereof, -(CH2)2CH3C1, -CH2N+(CH3)2(CH2)CH3C1- or -CH2N+(CH3)2(CH2)21\14-(CH3)2(CH2), CH32Cr; 4 and a are respectively integers from 1 to 15, preferably 1-11.
R4 is selected from H or a methyl group; Gr is -OH or -0-Na ; m and n represent the molar percentage of the structural units among the entire amphiphilic macromolecule repeating unit, and m is 70-99mo1%, preferably 70-90mol%, more preferably 70-mol%; n is 1-30mol%, preferably 2-28mo1%, more preferably 20-28mol%.
In another embodiment, in formula (2), R1-R3 is preferably H, Gr is preferably -0-Na .
In another embodiment, the highly sterically hindered structural unit B
contains at least a structure Q wherein the structure G is a cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain, or is selected from a structure of formula (3), and the highly sterically hindered structural unit B
optionally contains a structure of formula (4):
R
I
CH2-C --)---(- CH2 - C 1---0 = C
I
\\:......,,z,...\,, formula (3) formula (4) In formula (3), R5 is H or a methyl group; preferably H; R6 is a radical selected from the group consisting of the structures of formulas (5) and (6).
/CH2 -0(CH2).CH, / \
CH2 - 0(CH2)2COOCH2CH3 CH2 -0(CH2).CH3 \ /
CH2 - 0(CH2).CH3 ¨ NH ¨C -- CH2¨ 0(CH2)2COOCH2CH3 cH2 - 0 -CH
\ \
CH2 - 0(CH2).CH3 CH, - 0(CH2)2COOCH2CH3 formula (5) , and formula (6) In formula (5), a is an integer from 1 to 11; preferably 1-7;
In formula (4), R7 is H; R8 is selected from H, -S03H and salts thereof, -(CH2)2CH3C1, -CH2N+(CH3)2(CH2)CH3C1- or -CH2N+(CH3)2(CH2)21\14-(CH3)2(CH2), CH32Cr; 4 and a are respectively integers from 1 to 15, preferably 1-11.
4 , International Application Number: PCT/CN2011/001579 , . .
Preferably, the highly sterically hindered structural unit B comprises a structure G and a structure of formula (4).
In another embodiment, the cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain is selected from the group consisting of:
¨r¨CH--CH¨CH-¨ I I CH2 I H2C\ / C112 \ /
H2C\ /CH2 CH r c 1 .0 =
112NHCOCH3, and , .
Preferably, the molar percentage of structure G of the highly sterically hindered structural unit B in the entire amphiphilic macromolecule repeating units is 0.02-2mol%; preferably 0.02-1.0mol%, more preferably 0.05-0.5 mol%.
Preferably, the molar percentage of the structure of formula (4) of the highly sterically hindered structural unit B in the whole amphiphilic polymer repeat units is 0.05-5mol%; preferably 0.1-2.5mol%, more preferably 0.15-0.75mol%.
In another embodiment, the highly sterically hindered structural unit B has a structure of formula (7):
I x H-G)-(Cf12-C -1-x Y
I
=====\.=
R8 formula (7).
In formula (7), the definition on G is as described above, preferably the structure -r-CH ¨
¨CH¨CH--CH¨CH¨ I IH2C CH2 /
\ \ /
H2C\ /C1-12 CH r C I NHCO =
of formula (3), H2 , NHCOCH3 or ; the definitions on R7 and R8 are as described in formula (4); x and y represent the molar percentages of the structures in the entire amphiphilic macromolecule repeating units, and x is 0.02-2mol%, preferably 0.02-1.0mol%, more preferably 0.05-0.5mol%; y is 0.05-5mol%, preferably 0.1-2.5mol%, and more preferably 0.15-0.75mo1%.
International Application Number: PCT/CN2011/001579 In another embodiment, the amphiphilic structural unit C has a structure of formula (8):
\
=--C
formula (8) In formula (8), R9 is H or a methyl group; R10 is -0- or -NH-; R11 is a radical containing a straight-chain hydrocarbyl, a branched hydrocarbyl, a polyoxyethylene (PEO) group, a polyoxypropylene (PPO) group, an E0 and PO block, a mono-quaternary ammonium salt, a multiple-quaternary ammonium salt or a sulfonic acid and salts thereof.
Preferably, the molar percentage of the amphiphilic structural unit C in the entire amphiphilic macromolecule repeating units is 0.05-10mol%; preferably 0.1-
Preferably, the highly sterically hindered structural unit B comprises a structure G and a structure of formula (4).
In another embodiment, the cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain is selected from the group consisting of:
¨r¨CH--CH¨CH-¨ I I CH2 I H2C\ / C112 \ /
H2C\ /CH2 CH r c 1 .0 =
112NHCOCH3, and , .
Preferably, the molar percentage of structure G of the highly sterically hindered structural unit B in the entire amphiphilic macromolecule repeating units is 0.02-2mol%; preferably 0.02-1.0mol%, more preferably 0.05-0.5 mol%.
Preferably, the molar percentage of the structure of formula (4) of the highly sterically hindered structural unit B in the whole amphiphilic polymer repeat units is 0.05-5mol%; preferably 0.1-2.5mol%, more preferably 0.15-0.75mol%.
In another embodiment, the highly sterically hindered structural unit B has a structure of formula (7):
I x H-G)-(Cf12-C -1-x Y
I
=====\.=
R8 formula (7).
In formula (7), the definition on G is as described above, preferably the structure -r-CH ¨
¨CH¨CH--CH¨CH¨ I IH2C CH2 /
\ \ /
H2C\ /C1-12 CH r C I NHCO =
of formula (3), H2 , NHCOCH3 or ; the definitions on R7 and R8 are as described in formula (4); x and y represent the molar percentages of the structures in the entire amphiphilic macromolecule repeating units, and x is 0.02-2mol%, preferably 0.02-1.0mol%, more preferably 0.05-0.5mol%; y is 0.05-5mol%, preferably 0.1-2.5mol%, and more preferably 0.15-0.75mo1%.
International Application Number: PCT/CN2011/001579 In another embodiment, the amphiphilic structural unit C has a structure of formula (8):
\
=--C
formula (8) In formula (8), R9 is H or a methyl group; R10 is -0- or -NH-; R11 is a radical containing a straight-chain hydrocarbyl, a branched hydrocarbyl, a polyoxyethylene (PEO) group, a polyoxypropylene (PPO) group, an E0 and PO block, a mono-quaternary ammonium salt, a multiple-quaternary ammonium salt or a sulfonic acid and salts thereof.
Preferably, the molar percentage of the amphiphilic structural unit C in the entire amphiphilic macromolecule repeating units is 0.05-10mol%; preferably 0.1-
5.0mol%, more preferably 0.2-1.7mol%.
In another embodiment, the structures consisted of R10 and R11 can be selected from -0(CH2)gN+(CH3)2(CH2)hCH3X -NH(CH2),N
(CH3)2(CH2)JCH3X-, -0(CH2)kNl((CH2)/CH3)p)C, -0(CH2),IN
(CH3)2(CH2)aCH(S 03H) CH2(E0)0(P0)7(CH2)6CH3X-, -NH(CH2),,INIICH3)2(CH2),,CH(S03H) CH2(E0)0(P0)7(CH2)8CH3X", -0(CH2),IN
(CH3)2(CH2)aCH(C00H) CI-12(E0)/3(P0)7(CH2)6CH3X", -NH(CH2)(IN+(CH3)2(CH2),CH(C00H) CH2(E0)0(P0)7(CH2),5CH3X-, -0(CH2)2N+(CH3)2(CH2)ES03-, -(0CH(CH2N (CH3)2(CH2)CH3COCH2)10(CH2)0CH3, -(0CH(CH2N1((CH2)xCH3)3C1 )CH2),O(CH2)KCH3, -0CH(CH2N+(CH3)2(CH2),CH3X"))2, -0CH(CH2N ((CH2)CH3)3X ))2 ;
wherein, g, i, k and q are respectively integers of 1-6, preferably 2-4; h and j are respectively integers of 3-21, preferably 3-17; p is an integer of 3-9, preferably 3-5; a is an integer of 1-12, preferably1-8; 13 and y are respectively integers of 0-40, 13 is preferably 0-25, y is preferably 0-15; is an integer of 0-21, preferably 0-17;
c is an integer of 4-18, preferably 4-12; is an integer of 1-21, preferably 1-15; n and I are
In another embodiment, the structures consisted of R10 and R11 can be selected from -0(CH2)gN+(CH3)2(CH2)hCH3X -NH(CH2),N
(CH3)2(CH2)JCH3X-, -0(CH2)kNl((CH2)/CH3)p)C, -0(CH2),IN
(CH3)2(CH2)aCH(S 03H) CH2(E0)0(P0)7(CH2)6CH3X-, -NH(CH2),,INIICH3)2(CH2),,CH(S03H) CH2(E0)0(P0)7(CH2)8CH3X", -0(CH2),IN
(CH3)2(CH2)aCH(C00H) CI-12(E0)/3(P0)7(CH2)6CH3X", -NH(CH2)(IN+(CH3)2(CH2),CH(C00H) CH2(E0)0(P0)7(CH2),5CH3X-, -0(CH2)2N+(CH3)2(CH2)ES03-, -(0CH(CH2N (CH3)2(CH2)CH3COCH2)10(CH2)0CH3, -(0CH(CH2N1((CH2)xCH3)3C1 )CH2),O(CH2)KCH3, -0CH(CH2N+(CH3)2(CH2),CH3X"))2, -0CH(CH2N ((CH2)CH3)3X ))2 ;
wherein, g, i, k and q are respectively integers of 1-6, preferably 2-4; h and j are respectively integers of 3-21, preferably 3-17; p is an integer of 3-9, preferably 3-5; a is an integer of 1-12, preferably1-8; 13 and y are respectively integers of 0-40, 13 is preferably 0-25, y is preferably 0-15; is an integer of 0-21, preferably 0-17;
c is an integer of 4-18, preferably 4-12; is an integer of 1-21, preferably 1-15; n and I are
6 International Application Number: PCT/CN2011/001579 respectively integers of 1-30, preferably 1-20; 0 and ic are respectively integers of 3-21, preferably 3-17; k is an integer of 0-9, preferably 0-5; r is an integer of 3-21, preferably 3-17; s is an integer of 3-9, preferably 3-5; and X- is Cl- or Br-.
In another embodiment, the amphiphilic macromolecule has a structure of formula (9):
I
I
¨CH2¨Cil)¨(CH2 C) ______________ G-H-cH2 C __ ) I m n x Y
I z 0=C 0=C 0=C
I INH2A Rio Ri R :
8 , Formula (9) In formula (9), the definitions on R4, m and n are as described in formula (2); the definitions on R7, R,s, G X and y are as described in formula (7); the definitions on R9, R10 and R11 are as described in formula (8); z represents the molar percentage of this structural unit in the entire amphiphilic polymer repeat unit, and z is 0.05-10 mol%, preferably 0.1-5.0mol%, more preferably 0.2-1.7mol%.
Specifically, this present invention provides a high molecular compound having a structure of formulas (I)-(X):
F
4cH2 ).(cH27)__141HT_H0H2_cH4;_l{cH274 n C=0 C=0 H2C CH2 1=0 c NH2 0-Na* H2 e Br N
/1:C H3 A B c c H3 L-(I)
In another embodiment, the amphiphilic macromolecule has a structure of formula (9):
I
I
¨CH2¨Cil)¨(CH2 C) ______________ G-H-cH2 C __ ) I m n x Y
I z 0=C 0=C 0=C
I INH2A Rio Ri R :
8 , Formula (9) In formula (9), the definitions on R4, m and n are as described in formula (2); the definitions on R7, R,s, G X and y are as described in formula (7); the definitions on R9, R10 and R11 are as described in formula (8); z represents the molar percentage of this structural unit in the entire amphiphilic polymer repeat unit, and z is 0.05-10 mol%, preferably 0.1-5.0mol%, more preferably 0.2-1.7mol%.
Specifically, this present invention provides a high molecular compound having a structure of formulas (I)-(X):
F
4cH2 ).(cH27)__141HT_H0H2_cH4;_l{cH274 n C=0 C=0 H2C CH2 1=0 c NH2 0-Na* H2 e Br N
/1:C H3 A B c c H3 L-(I)
7 International Application Number: PCT/CN2011/001579 . .
' I . -1--(CH2 IH __________________ )m(2 r )ItH-r ) (CH2 CH-)---j-(CH2¨Cr4 n x 1=0 =------0 H 2C \ /CH2 I.
I C =0 C H I
NH2 0-Na*
se: C H2 N CI ;
N-,--6' e Br H3c CHi /
- I m '3 - \
i H3C/ j CH3 I i H2 i -I-A B c CH3 _ (II) , ------------------------------------------4CH2-CH )m (CH2 CH _______________ )n I I ( CH-CH ) (CH2 CH
) (CH2¨CH) I Ix Y I z r----- 0 C =0 H2C\ /C H2 I CH
I
NH2 0-Na* 0 I
I
NH
I H2C¨C¨CH2 C=0 le e leBr e N Br 10 e hCI
H3CMC H3 H3C<A,J1 C/
- 4õ 1 CH2 CHr '33 CHr '3 4-1--_ (III) , ¨(cH2cH )¨ (CH2 r ) ( CH2 r __ ) (cH2 cH+_,_(cH2_,F,__)_ 1 - n 1 z 1_0 r_o i, 0 ro NH2 0-Na.- 0 SO3Na ' leBre H2C ¨fi ¨CH2 N
IH3C/4> CH3 H2C ¨C -I C( - I 1 CH2 H2C -19 _r Cr 0 I I
I I I
A B c
' I . -1--(CH2 IH __________________ )m(2 r )ItH-r ) (CH2 CH-)---j-(CH2¨Cr4 n x 1=0 =------0 H 2C \ /CH2 I.
I C =0 C H I
NH2 0-Na*
se: C H2 N CI ;
N-,--6' e Br H3c CHi /
- I m '3 - \
i H3C/ j CH3 I i H2 i -I-A B c CH3 _ (II) , ------------------------------------------4CH2-CH )m (CH2 CH _______________ )n I I ( CH-CH ) (CH2 CH
) (CH2¨CH) I Ix Y I z r----- 0 C =0 H2C\ /C H2 I CH
I
NH2 0-Na* 0 I
I
NH
I H2C¨C¨CH2 C=0 le e leBr e N Br 10 e hCI
H3CMC H3 H3C<A,J1 C/
- 4õ 1 CH2 CHr '33 CHr '3 4-1--_ (III) , ¨(cH2cH )¨ (CH2 r ) ( CH2 r __ ) (cH2 cH+_,_(cH2_,F,__)_ 1 - n 1 z 1_0 r_o i, 0 ro NH2 0-Na.- 0 SO3Na ' leBre H2C ¨fi ¨CH2 N
IH3C/4> CH3 H2C ¨C -I C( - I 1 CH2 H2C -19 _r Cr 0 I I
I I I
A B c
8 , International Application Number: PCT/CN2011/001579 , .
(IV) i 4cH2 r ) (CH2 111)71 ( CH2 CH ) (CH2- H-)---1-(CH2-14 I x 1=-0 1=0 C=--0 I 1101 C=0 oI
NH2 0-Na' lijii¨k.
H,C C CH2 TI612 C c., ol I
c., 1 .3c----7--c.3 3re 1 O 0 cH2 /
1 .3 CH, 1 H3c ¨
r I I CH2 , CH, r !i,Q, CF CH, ,T.
cH2 1 I I CH, CH2 H3C/ I \ CH3 0=C
I C=0 I
lo ? o I
I 0 cI1-12 CH2 Li, cH3 _ CH, I
cu3 A B C
(V) , ------------------------------------------------------------ ----- ¨ . _ 4cH2¨CH ) (CH2 CH1)-7 1--ECH-CH ) (CH2-CH-Y----/C H2-7 )7 I m I I I x I
1 . H2C /cH2 c I
NH2 0-Na* H2 0 CH2 l H2C¨C ¨CH2 e CI e N
le e H3C ICH3 H3c, NI \Hr /Ni Hre __________________________________________________________ nj-I3C I \
CIH2 CH2-'"3 CHu?"3 ,¨r- --r cH3 cH3 cH3 A B C
, ¨
(VI) r ----------------------------------------H ) m 2 I I z --==.-0 C-=-0 0 H2C\ / CH2 i -'------0 I
CH
NH2 0-Na+
I i I
I .1 a ; N Br . H3C' NI -.....-..tH31 N3c, CH3 CH2 : I I 4H2 1 CH3 :
A B : C CH3 L-(VII)
(IV) i 4cH2 r ) (CH2 111)71 ( CH2 CH ) (CH2- H-)---1-(CH2-14 I x 1=-0 1=0 C=--0 I 1101 C=0 oI
NH2 0-Na' lijii¨k.
H,C C CH2 TI612 C c., ol I
c., 1 .3c----7--c.3 3re 1 O 0 cH2 /
1 .3 CH, 1 H3c ¨
r I I CH2 , CH, r !i,Q, CF CH, ,T.
cH2 1 I I CH, CH2 H3C/ I \ CH3 0=C
I C=0 I
lo ? o I
I 0 cI1-12 CH2 Li, cH3 _ CH, I
cu3 A B C
(V) , ------------------------------------------------------------ ----- ¨ . _ 4cH2¨CH ) (CH2 CH1)-7 1--ECH-CH ) (CH2-CH-Y----/C H2-7 )7 I m I I I x I
1 . H2C /cH2 c I
NH2 0-Na* H2 0 CH2 l H2C¨C ¨CH2 e CI e N
le e H3C ICH3 H3c, NI \Hr /Ni Hre __________________________________________________________ nj-I3C I \
CIH2 CH2-'"3 CHu?"3 ,¨r- --r cH3 cH3 cH3 A B C
, ¨
(VI) r ----------------------------------------H ) m 2 I I z --==.-0 C-=-0 0 H2C\ / CH2 i -'------0 I
CH
NH2 0-Na+
I i I
I .1 a ; N Br . H3C' NI -.....-..tH31 N3c, CH3 CH2 : I I 4H2 1 CH3 :
A B : C CH3 L-(VII)
9 , , ---------- - ----------------------- --------- -- i --- --- -- ----I--(CH, 111 ).(CH2-111-H ( CH2-IH ) (CH2 ¨CH¨Ft CH2-1114;
N i1,1 H, 0-Na' TH I HA-1-114z CH SO,Na CH2 18re 1 I 2T T / '',CH, H2 i 7H2 H,C ¨ ¨
siLi' Cr' Iti' CH, 0,.......--? 1 C="0 1112 i I
et.µ 7H2 r CH, CH, A B C
(VIII) , -------------------------------------------, (CH2 CH ) (c-1H ) --+ H¨ H44CH2¨CH ) (CH2¨ F.14-I m n x Y ? X
C=--0 1.0 ,,2,,c,_,, =
NH2 0-Na* CH2 e 0 io 4-NHC0CH3 ,...Na...., H3C I CH3 Cl-i2 7H2 e var N CI /N
H3Ci I Cl-i3 H3C ¨
T a H2 k -.1-A. B C
_____________________ or MO
¨(cH, 1H ____ )(cH2 IH--)--41H¨CH CH2 H) ; (CH2¨CH)--m n : I -7' k y , 1 z i=c, ,=-...----0 i H2C\ 1H2 4 i C
NH2 0-Na+ i 112 i (1) 'I. SO3Na L
; H2C ¨C ¨CH2 1.H 6 e i i N
3C s/-1 r N Br o 1 ,4Cht3 E.1Li13C CH3 t2 I
A i , B .
. C
One aspect of the invention relates to an amphiphilic macromolecule comprising, as repeating units, a structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics, a highly sterically hindered structural unit B
and an amphiphilic structural unit C, wherein the highly sterically hindered structural unit B
comprises a structure G and a structure of formula (4), wherein the structure G is a cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain, or is selected from a structure of formula (3):
Rs "i CH2 C
0 =-C
formula (3) formula (4) wherein in formula (3), R5 is H or a methyl group; R6 is a radical selected from the group consisting of the structures of formula (5) and formula (6):
zcH2-0(ci)acH3 cH2¨ 0 ¨CH
CCH2 ¨0(CH2).CH3 /H2 0(CH2)2COOCH2CH3 /H2 ¨ 0(CH2).CII3 ¨NH¨C ¨CH2¨ 0(CH2)2COOCH2CH3 cu2-0 ¨CH
CH2 ¨0(CH2),CH3 CH2 ¨ 0(CH2)2COOCH2CH3 formula (5) formula (6) in formula (5), a is an integer from 1 to 11, in formula (4), R7 is H; R8 is selected from the group consisting of H, -S03H
and salts thereofõ -(CH2)2CH2C1, -CH21\1+(CH3)2(CH2)CH3C1- and -CH2N+(CH3)2 (CH2)2N+(CH3)2(CH2)aCH3 20"; 4 and a are respectively integers from 1 to 15.
The molecular weight of the amphiphilic macromolecule described above is 10a International Application Number: PCT/CN2011/001579 between 1,000,000 and 20,000,000; preferably between 3,000,000 and 14,000,000.
The measurement of the molecular weight M is as follows: The intrinsic viscosity [77] is measured by Ubbelohde viscometer as known in the art, then the obtained intrinsic viscosity [77] value is used in the following equation to obtain the desired molecular weight M:
M = 802 [1711:25 The amphiphilic macromolecule according to this present invention can be prepared by known methods in the art, for example, by polymerizing the structural unit for adjusting molecular weight, molecular weight distribution and charge characteristics, the highly sterically hindered structural unit and the amphiphilic structural unit in the presence of an initiator. The polymerization process can be any type well known in the art, such as, suspension polymerization, emulsion polymerization, solution polymerization, precipitation polymerization, and etc.
A typical preparation method is as follows: the above monomers are each dispersed or dissolved in an aqueous system under stirring, the monomer mixture is polymerized by the aid of an initiator under nitrogen atmosphere to form the amphiphilic macromolecule. The so far existing relevant technologies for preparing an amphiphilic macromolecule can all be used to prepare the amphiphilic macromolecule of this invention.
All the monomers for preparing the amphiphilic macromolecule can be commercially available, or can be prepared on the basis of prior art technology directly; and some monomers' synthesis are described in details in specific examples.
Description of Figures Figure 1 depicts the relationship of viscosity vs. concentration of the amphiphilic macromolecules obtained from examples 1-5 of the invention in saline having a degree of mineralization of 2 x104mg/L at a temperature of 800.
Figure 2 depicts the relationship of viscosity vs. temperature of the amphiphilic macromolecules obtained from the examples 1-5 of the invention in saline having a International Application Number: PCT/CN2011/001579 degree of mineralization of 3x104mg/L at the concentration of 1750mg/L
Detailed Description of the Invention The present invention is further illustrated below by combining specific examples; however, this invention is not limited to the following examples.
Example 1 This example synthesized the amphiphilic macromolecule of formula (I):
4CH2 H ) (CH2 CH-Y-14CH¨CH-L¨(CH2¨CH+¨j-(CH2¨CH---)-I n I I ix I z C=0 C=0 H2C CH2 c NH2 0-Na+H2 9 __________________________________________________ e Br N, A B c CH 3 L_ (I) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 78%, 20%, 0.25%, 0.5%, 1% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 22 E; after 5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 1360 x104.
International Application Number: PCT/CN2011/001579 Example 2 This example synthesized the amphiphilic macromolecule of formula (II).
¨(CH2 H (CH2 H _______ +hi CH ) (CH2 CH+¨j-(C CHH2¨
x Y z ?=0 H2C\ /CH2 , o CH
NH2 0-Na' e I cH2 L
isi",1713r Cl-!2 j H3C
CH3 j A c cH3 (II) = _______________________________________ ) CH, NH
The synthesis route of the monomer was as follows:
H3cõci ) _____________________________________________ CH3 I
DCM, Et3NI, le . NH2 O NH
The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 73%, 25%, 0.15%, 0.15%, 1.7% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 8, then nitrogen gas was introduced in for 40 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 25E; after 5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 1010x104.
International Application Number: PCT/CN2011/001579 Example 3 This example synthesized the amphiphilic macromolecule of formula (III):
)m I (CH2 CH )n I I ¨ECH-CH ) x 40 (CH2 CH-Y¨ (01-32¨H-H2z-C=0 C 0-Na+ H2C CH2 C=0 CH o N
NH
CH2 H 2C ¨C ¨C H2 le CP 6 _H e NBr N Br 3H C<_I__\ m/1\
CHP^33C CHPH3 cH3 cH3 A B cH3 (III) NH
The synthesis route of the monomer was as follows:
Ilk NH2 Ph NH
DCM0, Et3N
The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 24.5%, 0.15%, 0.15%, 0.2% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 25E ; after 6 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 660x104.
International Application Number: PCT/CN2011/001579 = .
Example 4 This example synthesized the amphiphilic macromolecule of formula (IV):
--(CH2 CH ) (CH2 1-+-1 ( CH2 r ).(CH2 CH44(CH2-CH-+
C=--0 =_-(:) I z I
(1 40 NH2 0-Na )' i So3Na ' I
6 e ; I H2c¨C----CH2 H N r I I
' /1 CH3 ? CH2 = .2C-CCH2 li2C-C-1CH2 j I I I
C
A B C
(IV) H/LI2---044'+cH, q riH,C-0-C\
H2C=C-C-0 -CH
H2-.01-C21-CH3 -12 , The synthesis route of the monomer 0-(4 CH
q was as follows:
International Application Number: PCT/CN2011/001579 CH,OH
110 KOH Bu4N* IFI . .
DCM ' o 0¨EC42 11 I
c H, IHH
KOH &Or rH OH Hc¨c2---o¨e .
---...
DCM
.1210 4',__!___2___::,_-_ H
0¨C
I
, .
(CHd2SO4 OCH, HCr¨CH, ¨0¨CH, .-K,CO3, DMF
.1,-0¨,----j---2.:10.--'12 lit H, õ,L1-04--12-Y_ ii, CH, H/
H,C C-0¨C.,,, 4,4 ¨0¨C
s'...¨OH Br(CHACH3 H , F)F,04 ------'' H,CO-H/ C ___ ' 113CO-HC T ,r Pd/C, &OH \ C12-0H
H,C ¨0 ¨8-,, -'0-0H C-044'24CH, H, H2 q Hõ,./C ,.....,,_ H2C---0--C q Na0H, Et0H / .-...'"Fi 4¨ 'c¨)-cr o ri 2 ___ - HO-HC y , H,C==--C-0-EiC
\ H )C4'-0-FICI'l-CH, Davi, Et31,1 ,c . ti,.)2=04412 -)-cr, - /4 q FiT" -FC2-+,1CH3 FiT-0-0'--)-qCH, The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.05%, 0.5%, 1.45% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 25 0 ; after 6 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 370 x 104.
International Application Number: PCT/CN2011/001579 . .
Example 5 This example synthesized the amphiphilic macromolecule of formula (V):
, 4 CH2 r MCH2 11-1" T)T¨j ( CH2 tH )x (CH2¨ H¨)---;-(CH2-Y
r-- 0=--0 C=0 .H2 0Na NH 0 1 CH2 e ___.
H,C ----C ¨CH2 I Cl CH2 I I
H3C- I -CH3 's.) 63re /
I 0 I H 3C __ CH3 CH, I
CHr 1CH2 3:, CP 012 I
CH2 I NH t c.2 1 1 c,,i2 I
H3c/1\cH3 cH, 0c 1 c=õ0 cH2 I c=___0 1 I
1 0 cH2 cH2 1 1 c,3 ICH, ICH3 A B C
c- - = ----------------------- J --- (V) H,C 0 FCI2 'CI' 11 0 FC12 CH3 rl ry / H2 H2 H2 rl H2 The synthesis route of the monomer H
was as follows:
/ \
H2N(....--- , OH choxane, KOH reflux __________________________________ T. H2N ____ CN Et0H, H2SO4¨(--_________________________ OH CN
\ ______________________________________________ /
00C CH2CH3 COOCH,CH, nrCI
H2N ___________________ (-----,...õØõ.,\õ,,,C0OCH2CH3 0 HN--(----N.000OCH2CH, DCM, Et3N
0 \ , C H,CH3 COOCH2CH, The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 78%, 21%, 0.1%, 0.1%, 0.8%
in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, International Application Number: PCT/CN2011/001579 then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 25 E ; after 6 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 450x 104.
Example 6 This example synthesized the amphiphilic macromolecule of formula (VI):
( CH¨CH ) (CH2 C H2 CH ) (CH2 CH ) m I n I x =0 C=0 H2C CH2 c C=0 o1 NH2 0-Na* H2 CH2 ;
H2C ¨C ¨CH2 e Cl je e N 13rÃ-) N Br H3C.1 /1\
CH3 1.13c / \
CH2 ; C HPF4;13C C HP H3 ;
CH3 ;
A
(VI) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 73%, 25%, 0.5%, 0.5%, 1% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 45 ; after 3 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered International Application Number: PCT/CN2011/001579 amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 640 x104.
Example 7 This example synthesized the amphiphilic macromolecule of formula (VII):
--(CH2 CH )m (CH2 CH CH¨H ) x I (CH2 CH ) j(CH2¨CH--)-n I z r-O H2C\ /CH2 CH
NF-12 0-Na' NH
CF-f2 CH2 I Cl e - ()Bre = r cH3 (VII) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.25%, 0.5%, 1.25% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 55 0; after 3 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 107x 104.
International Application Number: PCT/CN2011/001579 Example 8 This example synthesized the amphiphilic macromolecule of formula (VIII):
CH ) (CH2 CH)-1 ( CH2 r (CH2¨CH--)---4(CH274 m n y ?=040 1=0 c=0 NH2 0 Ha. NH 0 H2c ____________________ 7 ___________________________ cH2 S03Na CH2 Br cH2 H3c ____________________________________________ C H. r r2 c,H2 9=0 cH2 H2 r cH3 cH, A
(VIII) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 70%, 28%, 0.15%, 0.75%, 1.1% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 55 E ; after 3 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 310x104.
International Application Number: PCT/CN2011/0015 79 Example 9 This example synthesized the amphiphilic macromolecule of formula (IX):
¨(cH2¨cH )m (CH2 r _________________ tH1H-HCH2¨CH
=0 T=0 HC\ /CH2 o NH2 0-Na+ TH
CH2 e I e a NHCOCH3 ,N, 4-" e N r /I
N\
CI /rcH3 H3CCH3 H30_ A
(IX) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23.5%, 0.5%, 0.2%, 0.8%
in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 500; after 2.5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 720x104.
Example 10 This example synthesized the amphiphilic macromolecule of formula (X):
International Application Number: PCT/CN2011/001579 --(CH2 (CH2¨CH __ 4CH¨CH+(C1-12¨ H __ (CH2 CH)--m n x z 1=0 H2O\ /CH2 C=0 NH2 0-Na H2 SO3Na H2O¨Fi¨c, H2 e N Sr¨(,) N Br -i4\
7.7_,C1-413C ¨1¨"uCH3 (X) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.5%, 0.5%, 1% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 50E ; after 2 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 520x 104.
Measurement Examples Measurement Example 1 Saline having a mineralization degree of 2x104mg/L was used to prepare amphiphilic macromolecule solutions with different concentrations, and the relationship between the concentration, temperature and the viscosity of the solution was determined. The results were shown in Figure 1 and Figure 2.
The figures showed that the amphiphilic macromolecule solutions of examples International Application Number: PCT/CN2011/001579 1-5 still have favorable viscosifying capacity under the condition of high temperature and high degree of mineralization. The highly sterically hindered unit in the amphiphilic macromolecule reduced the rotational degree of freedom in the main chain and increased the rigidity of the macromolecule chain, which made the macromolecule chain difficult to curl and tend to stretch out, thus enlarging the hydrodynamic radius of the macromolecule; in the meantime, the amphiphilic structural unit associated each other to form the microdomain by intramolecular- or intermolecular- interaction, thus enhancing the viscosifying capacity of the solution remarkably under the conditions of high temperature and high salinity.
Measurement Example 2 Testing method: Under a testing temperature of 25 , 25m1 electric dehydration crude oil samples from three types of oilfields were added in a 50m1 test tube with a plug, then 25ml aqueous solutions of amphiphilic macromolecule with different concentrations formulated with distilled water were added in. The plug of the test tube was tightened, then the test tube was shaken manually or by using an oscillating box for 80-100 times in horizontal direction, and the shaking amplitude should be greater than 20cm. After sufficient mixing, the plug of the test tube was loosed.
Viscosity reduction rate for crude oil was calculated according to the following equation:
viscosity of crude oil sample - viscosity after mixing Viscosity reduction rate(%) ¨x 100 viscosity of crude oil sample Table 1: Experimental results of the heavy oil viscosity reduction of the amphiphilic macromolecule obtained from the example 6 to example 10 (oil-water ratio 1:1, 25E) oil-water volume ratio oil viscosity oil viscosity oil viscosity (1:1) sample reduction sample reduction sample reduction test temperature 1 rate (%) 2 rate (%) 3 rate (%) (25 C) initial viscosity 900 7400 12000 International Application Number: PCT/CN2011/001579 (mPa-s) 400mg/L 405 55.00 1900 74.32 3300 72.50 600mg/L 320 64.44 1350 81.76 2450 79.58 Example 800mg/L 275 69.44 1040 85.95 1250 89.58 1000mg/L 245 72.78 740 90.00 850 92.92 1200mg/L 220 75.56 670 90.95 725 93.96 400mg/L 475 47.22 2100 71.62 3500 70.83 600mg/L 375 58.33 1750 76.35 2600 78.33 Example 800mg/L 290 67.78 1475 80.07 1350 88.75 1000mg/L 230 74.44 1050 85.81 900 92.50 1200mg/L 230 74.44 805 89.12 775 93.54 400mg/L 535 40.56 1690 77.16 3150 73.75 600mg/L 460 48.89 1100 85.14 1900 84.17 Example 800mg/L 390 56.67 780 89.46 1125 90.63 1000mg/L 350 61.11 690 90.68 850 92.92 1200mg/L 330 63.33 630 91.49 710 94.08 400mg/L 470 47.78 1800 75.68 3600 70.00 600mg/L 390 56.67 1480 80.00 2400 80.00 Example 800mg/L 310 65.56 975 86.82 1370 88.58 1000mg/L 260 71.11 675 90.88 1025 91.46 1200mg/L 230 74.44 580 92.16 840 93.00 400mg/L 505 43.89 1600 78.38 3800 68.33 600mg/L 425 52.78 1150 84.46 2350 80.42 Example 800mg/L 350 61.11 825 88.85 1275 89.38 1000mg/L 315 65.00 695 90.61 1000 91.67 1200mg/L 280 68.89 625 91.55 825 93.13 Table 1 showed that the amphiphilic macromolecules of examples 6-10 had good International Application Number: PCT/CN2011/001579 effects for viscosity reduction as to all three oil samples. With the increase of the concentration of the amphiphilic macromolecule solution, the viscosity reduction rate increased. And, when the concentration of the amphiphilic macromolecule solution was the same, the viscosity reduction rate increased with the enhancing of the viscosity of the oil sample. It was believed that the amphiphilic macromolecule could reduce the viscosity of the crude oil remarkably via a synergetic effect between the highly sterically hindered structural unit and the amphiphilic structural unit, which could emulsify and disperse the crude oil effectively.
Industrial Application The amphiphilic macromolecule of this invention can be used in oilfield drilling, well cementing, fracturing, crude oil gathering and transporting, sewage treating, sludge treating and papermaking, and it can be used as intensified oil producing agent and oil displacing agent, heavy oil viscosity reducer, fracturing fluid, clay stabilizer, sewage treating agent, retention aid and drainage aid and strengthening agent for papermaking.
The amphiphilic macromolecule of this invention is especially suitable for crude oil exploitation, for instance, it can be used as an intensified oil displacement polymer and a viscosity reducer for heavy oil. When it is used as an oil displacement agent, it has remarkable viscosifying effect even under the condition of high temperature and high salinity, and can thus enhance the crude oil recovery. When it is used as a viscosity reducer for heavy oil, it can remarkably reduce the viscosity of the heavy oil and decrease the flow resistance thereof in the formation and wellbore by emulsifying and dispersing the heavy oil effectively.
N i1,1 H, 0-Na' TH I HA-1-114z CH SO,Na CH2 18re 1 I 2T T / '',CH, H2 i 7H2 H,C ¨ ¨
siLi' Cr' Iti' CH, 0,.......--? 1 C="0 1112 i I
et.µ 7H2 r CH, CH, A B C
(VIII) , -------------------------------------------, (CH2 CH ) (c-1H ) --+ H¨ H44CH2¨CH ) (CH2¨ F.14-I m n x Y ? X
C=--0 1.0 ,,2,,c,_,, =
NH2 0-Na* CH2 e 0 io 4-NHC0CH3 ,...Na...., H3C I CH3 Cl-i2 7H2 e var N CI /N
H3Ci I Cl-i3 H3C ¨
T a H2 k -.1-A. B C
_____________________ or MO
¨(cH, 1H ____ )(cH2 IH--)--41H¨CH CH2 H) ; (CH2¨CH)--m n : I -7' k y , 1 z i=c, ,=-...----0 i H2C\ 1H2 4 i C
NH2 0-Na+ i 112 i (1) 'I. SO3Na L
; H2C ¨C ¨CH2 1.H 6 e i i N
3C s/-1 r N Br o 1 ,4Cht3 E.1Li13C CH3 t2 I
A i , B .
. C
One aspect of the invention relates to an amphiphilic macromolecule comprising, as repeating units, a structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics, a highly sterically hindered structural unit B
and an amphiphilic structural unit C, wherein the highly sterically hindered structural unit B
comprises a structure G and a structure of formula (4), wherein the structure G is a cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain, or is selected from a structure of formula (3):
Rs "i CH2 C
0 =-C
formula (3) formula (4) wherein in formula (3), R5 is H or a methyl group; R6 is a radical selected from the group consisting of the structures of formula (5) and formula (6):
zcH2-0(ci)acH3 cH2¨ 0 ¨CH
CCH2 ¨0(CH2).CH3 /H2 0(CH2)2COOCH2CH3 /H2 ¨ 0(CH2).CII3 ¨NH¨C ¨CH2¨ 0(CH2)2COOCH2CH3 cu2-0 ¨CH
CH2 ¨0(CH2),CH3 CH2 ¨ 0(CH2)2COOCH2CH3 formula (5) formula (6) in formula (5), a is an integer from 1 to 11, in formula (4), R7 is H; R8 is selected from the group consisting of H, -S03H
and salts thereofõ -(CH2)2CH2C1, -CH21\1+(CH3)2(CH2)CH3C1- and -CH2N+(CH3)2 (CH2)2N+(CH3)2(CH2)aCH3 20"; 4 and a are respectively integers from 1 to 15.
The molecular weight of the amphiphilic macromolecule described above is 10a International Application Number: PCT/CN2011/001579 between 1,000,000 and 20,000,000; preferably between 3,000,000 and 14,000,000.
The measurement of the molecular weight M is as follows: The intrinsic viscosity [77] is measured by Ubbelohde viscometer as known in the art, then the obtained intrinsic viscosity [77] value is used in the following equation to obtain the desired molecular weight M:
M = 802 [1711:25 The amphiphilic macromolecule according to this present invention can be prepared by known methods in the art, for example, by polymerizing the structural unit for adjusting molecular weight, molecular weight distribution and charge characteristics, the highly sterically hindered structural unit and the amphiphilic structural unit in the presence of an initiator. The polymerization process can be any type well known in the art, such as, suspension polymerization, emulsion polymerization, solution polymerization, precipitation polymerization, and etc.
A typical preparation method is as follows: the above monomers are each dispersed or dissolved in an aqueous system under stirring, the monomer mixture is polymerized by the aid of an initiator under nitrogen atmosphere to form the amphiphilic macromolecule. The so far existing relevant technologies for preparing an amphiphilic macromolecule can all be used to prepare the amphiphilic macromolecule of this invention.
All the monomers for preparing the amphiphilic macromolecule can be commercially available, or can be prepared on the basis of prior art technology directly; and some monomers' synthesis are described in details in specific examples.
Description of Figures Figure 1 depicts the relationship of viscosity vs. concentration of the amphiphilic macromolecules obtained from examples 1-5 of the invention in saline having a degree of mineralization of 2 x104mg/L at a temperature of 800.
Figure 2 depicts the relationship of viscosity vs. temperature of the amphiphilic macromolecules obtained from the examples 1-5 of the invention in saline having a International Application Number: PCT/CN2011/001579 degree of mineralization of 3x104mg/L at the concentration of 1750mg/L
Detailed Description of the Invention The present invention is further illustrated below by combining specific examples; however, this invention is not limited to the following examples.
Example 1 This example synthesized the amphiphilic macromolecule of formula (I):
4CH2 H ) (CH2 CH-Y-14CH¨CH-L¨(CH2¨CH+¨j-(CH2¨CH---)-I n I I ix I z C=0 C=0 H2C CH2 c NH2 0-Na+H2 9 __________________________________________________ e Br N, A B c CH 3 L_ (I) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 78%, 20%, 0.25%, 0.5%, 1% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 22 E; after 5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 1360 x104.
International Application Number: PCT/CN2011/001579 Example 2 This example synthesized the amphiphilic macromolecule of formula (II).
¨(CH2 H (CH2 H _______ +hi CH ) (CH2 CH+¨j-(C CHH2¨
x Y z ?=0 H2C\ /CH2 , o CH
NH2 0-Na' e I cH2 L
isi",1713r Cl-!2 j H3C
CH3 j A c cH3 (II) = _______________________________________ ) CH, NH
The synthesis route of the monomer was as follows:
H3cõci ) _____________________________________________ CH3 I
DCM, Et3NI, le . NH2 O NH
The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 73%, 25%, 0.15%, 0.15%, 1.7% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 8, then nitrogen gas was introduced in for 40 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 25E; after 5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 1010x104.
International Application Number: PCT/CN2011/001579 Example 3 This example synthesized the amphiphilic macromolecule of formula (III):
)m I (CH2 CH )n I I ¨ECH-CH ) x 40 (CH2 CH-Y¨ (01-32¨H-H2z-C=0 C 0-Na+ H2C CH2 C=0 CH o N
NH
CH2 H 2C ¨C ¨C H2 le CP 6 _H e NBr N Br 3H C<_I__\ m/1\
CHP^33C CHPH3 cH3 cH3 A B cH3 (III) NH
The synthesis route of the monomer was as follows:
Ilk NH2 Ph NH
DCM0, Et3N
The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 24.5%, 0.15%, 0.15%, 0.2% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 25E ; after 6 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 660x104.
International Application Number: PCT/CN2011/001579 = .
Example 4 This example synthesized the amphiphilic macromolecule of formula (IV):
--(CH2 CH ) (CH2 1-+-1 ( CH2 r ).(CH2 CH44(CH2-CH-+
C=--0 =_-(:) I z I
(1 40 NH2 0-Na )' i So3Na ' I
6 e ; I H2c¨C----CH2 H N r I I
' /1 CH3 ? CH2 = .2C-CCH2 li2C-C-1CH2 j I I I
C
A B C
(IV) H/LI2---044'+cH, q riH,C-0-C\
H2C=C-C-0 -CH
H2-.01-C21-CH3 -12 , The synthesis route of the monomer 0-(4 CH
q was as follows:
International Application Number: PCT/CN2011/001579 CH,OH
110 KOH Bu4N* IFI . .
DCM ' o 0¨EC42 11 I
c H, IHH
KOH &Or rH OH Hc¨c2---o¨e .
---...
DCM
.1210 4',__!___2___::,_-_ H
0¨C
I
, .
(CHd2SO4 OCH, HCr¨CH, ¨0¨CH, .-K,CO3, DMF
.1,-0¨,----j---2.:10.--'12 lit H, õ,L1-04--12-Y_ ii, CH, H/
H,C C-0¨C.,,, 4,4 ¨0¨C
s'...¨OH Br(CHACH3 H , F)F,04 ------'' H,CO-H/ C ___ ' 113CO-HC T ,r Pd/C, &OH \ C12-0H
H,C ¨0 ¨8-,, -'0-0H C-044'24CH, H, H2 q Hõ,./C ,.....,,_ H2C---0--C q Na0H, Et0H / .-...'"Fi 4¨ 'c¨)-cr o ri 2 ___ - HO-HC y , H,C==--C-0-EiC
\ H )C4'-0-FICI'l-CH, Davi, Et31,1 ,c . ti,.)2=04412 -)-cr, - /4 q FiT" -FC2-+,1CH3 FiT-0-0'--)-qCH, The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.05%, 0.5%, 1.45% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 25 0 ; after 6 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 370 x 104.
International Application Number: PCT/CN2011/001579 . .
Example 5 This example synthesized the amphiphilic macromolecule of formula (V):
, 4 CH2 r MCH2 11-1" T)T¨j ( CH2 tH )x (CH2¨ H¨)---;-(CH2-Y
r-- 0=--0 C=0 .H2 0Na NH 0 1 CH2 e ___.
H,C ----C ¨CH2 I Cl CH2 I I
H3C- I -CH3 's.) 63re /
I 0 I H 3C __ CH3 CH, I
CHr 1CH2 3:, CP 012 I
CH2 I NH t c.2 1 1 c,,i2 I
H3c/1\cH3 cH, 0c 1 c=õ0 cH2 I c=___0 1 I
1 0 cH2 cH2 1 1 c,3 ICH, ICH3 A B C
c- - = ----------------------- J --- (V) H,C 0 FCI2 'CI' 11 0 FC12 CH3 rl ry / H2 H2 H2 rl H2 The synthesis route of the monomer H
was as follows:
/ \
H2N(....--- , OH choxane, KOH reflux __________________________________ T. H2N ____ CN Et0H, H2SO4¨(--_________________________ OH CN
\ ______________________________________________ /
00C CH2CH3 COOCH,CH, nrCI
H2N ___________________ (-----,...õØõ.,\õ,,,C0OCH2CH3 0 HN--(----N.000OCH2CH, DCM, Et3N
0 \ , C H,CH3 COOCH2CH, The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 78%, 21%, 0.1%, 0.1%, 0.8%
in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, International Application Number: PCT/CN2011/001579 then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 25 E ; after 6 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 450x 104.
Example 6 This example synthesized the amphiphilic macromolecule of formula (VI):
( CH¨CH ) (CH2 C H2 CH ) (CH2 CH ) m I n I x =0 C=0 H2C CH2 c C=0 o1 NH2 0-Na* H2 CH2 ;
H2C ¨C ¨CH2 e Cl je e N 13rÃ-) N Br H3C.1 /1\
CH3 1.13c / \
CH2 ; C HPF4;13C C HP H3 ;
CH3 ;
A
(VI) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 73%, 25%, 0.5%, 0.5%, 1% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 45 ; after 3 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered International Application Number: PCT/CN2011/001579 amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 640 x104.
Example 7 This example synthesized the amphiphilic macromolecule of formula (VII):
--(CH2 CH )m (CH2 CH CH¨H ) x I (CH2 CH ) j(CH2¨CH--)-n I z r-O H2C\ /CH2 CH
NF-12 0-Na' NH
CF-f2 CH2 I Cl e - ()Bre = r cH3 (VII) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.25%, 0.5%, 1.25% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 9, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 55 0; after 3 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 107x 104.
International Application Number: PCT/CN2011/001579 Example 8 This example synthesized the amphiphilic macromolecule of formula (VIII):
CH ) (CH2 CH)-1 ( CH2 r (CH2¨CH--)---4(CH274 m n y ?=040 1=0 c=0 NH2 0 Ha. NH 0 H2c ____________________ 7 ___________________________ cH2 S03Na CH2 Br cH2 H3c ____________________________________________ C H. r r2 c,H2 9=0 cH2 H2 r cH3 cH, A
(VIII) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 70%, 28%, 0.15%, 0.75%, 1.1% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH
value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed. The reaction was conducted at a temperature of 55 E ; after 3 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 310x104.
International Application Number: PCT/CN2011/0015 79 Example 9 This example synthesized the amphiphilic macromolecule of formula (IX):
¨(cH2¨cH )m (CH2 r _________________ tH1H-HCH2¨CH
=0 T=0 HC\ /CH2 o NH2 0-Na+ TH
CH2 e I e a NHCOCH3 ,N, 4-" e N r /I
N\
CI /rcH3 H3CCH3 H30_ A
(IX) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23.5%, 0.5%, 0.2%, 0.8%
in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 500; after 2.5 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 720x104.
Example 10 This example synthesized the amphiphilic macromolecule of formula (X):
International Application Number: PCT/CN2011/001579 --(CH2 (CH2¨CH __ 4CH¨CH+(C1-12¨ H __ (CH2 CH)--m n x z 1=0 H2O\ /CH2 C=0 NH2 0-Na H2 SO3Na H2O¨Fi¨c, H2 e N Sr¨(,) N Br -i4\
7.7_,C1-413C ¨1¨"uCH3 (X) The synthesis of the amphiphilic macromolecule of this example was as follows:
Firstly, water, accounting for 3/4 of the total weight of the reaction system, was charged into a reactor, then various monomers, totally accounting for 1/4 of the total weight of the reaction system, were charged into the reactor as well, and the molar percentages m, n, x, y, z for each repeating units were 75%, 23%, 0.5%, 0.5%, 1% in succession. The mixture was stirred until complete dissolution, and a pH
adjusting agent was then added in to adjust the reaction solution to have a pH value of about 8, then nitrogen gas was introduced in for 30 minutes to remove oxygen contained therein. An initiator was added into the reactor under the protection of nitrogen gas, and nitrogen gas was further continued for 10 minutes, then the reactor was sealed.
The reaction was conducted at a temperature of 50E ; after 2 hours, the reaction was ended with a complete conversion. After the drying of the obtained product, powdered amphiphilic macromolecule was obtained. The molecular weight of the amphiphilic macromolecule was 520x 104.
Measurement Examples Measurement Example 1 Saline having a mineralization degree of 2x104mg/L was used to prepare amphiphilic macromolecule solutions with different concentrations, and the relationship between the concentration, temperature and the viscosity of the solution was determined. The results were shown in Figure 1 and Figure 2.
The figures showed that the amphiphilic macromolecule solutions of examples International Application Number: PCT/CN2011/001579 1-5 still have favorable viscosifying capacity under the condition of high temperature and high degree of mineralization. The highly sterically hindered unit in the amphiphilic macromolecule reduced the rotational degree of freedom in the main chain and increased the rigidity of the macromolecule chain, which made the macromolecule chain difficult to curl and tend to stretch out, thus enlarging the hydrodynamic radius of the macromolecule; in the meantime, the amphiphilic structural unit associated each other to form the microdomain by intramolecular- or intermolecular- interaction, thus enhancing the viscosifying capacity of the solution remarkably under the conditions of high temperature and high salinity.
Measurement Example 2 Testing method: Under a testing temperature of 25 , 25m1 electric dehydration crude oil samples from three types of oilfields were added in a 50m1 test tube with a plug, then 25ml aqueous solutions of amphiphilic macromolecule with different concentrations formulated with distilled water were added in. The plug of the test tube was tightened, then the test tube was shaken manually or by using an oscillating box for 80-100 times in horizontal direction, and the shaking amplitude should be greater than 20cm. After sufficient mixing, the plug of the test tube was loosed.
Viscosity reduction rate for crude oil was calculated according to the following equation:
viscosity of crude oil sample - viscosity after mixing Viscosity reduction rate(%) ¨x 100 viscosity of crude oil sample Table 1: Experimental results of the heavy oil viscosity reduction of the amphiphilic macromolecule obtained from the example 6 to example 10 (oil-water ratio 1:1, 25E) oil-water volume ratio oil viscosity oil viscosity oil viscosity (1:1) sample reduction sample reduction sample reduction test temperature 1 rate (%) 2 rate (%) 3 rate (%) (25 C) initial viscosity 900 7400 12000 International Application Number: PCT/CN2011/001579 (mPa-s) 400mg/L 405 55.00 1900 74.32 3300 72.50 600mg/L 320 64.44 1350 81.76 2450 79.58 Example 800mg/L 275 69.44 1040 85.95 1250 89.58 1000mg/L 245 72.78 740 90.00 850 92.92 1200mg/L 220 75.56 670 90.95 725 93.96 400mg/L 475 47.22 2100 71.62 3500 70.83 600mg/L 375 58.33 1750 76.35 2600 78.33 Example 800mg/L 290 67.78 1475 80.07 1350 88.75 1000mg/L 230 74.44 1050 85.81 900 92.50 1200mg/L 230 74.44 805 89.12 775 93.54 400mg/L 535 40.56 1690 77.16 3150 73.75 600mg/L 460 48.89 1100 85.14 1900 84.17 Example 800mg/L 390 56.67 780 89.46 1125 90.63 1000mg/L 350 61.11 690 90.68 850 92.92 1200mg/L 330 63.33 630 91.49 710 94.08 400mg/L 470 47.78 1800 75.68 3600 70.00 600mg/L 390 56.67 1480 80.00 2400 80.00 Example 800mg/L 310 65.56 975 86.82 1370 88.58 1000mg/L 260 71.11 675 90.88 1025 91.46 1200mg/L 230 74.44 580 92.16 840 93.00 400mg/L 505 43.89 1600 78.38 3800 68.33 600mg/L 425 52.78 1150 84.46 2350 80.42 Example 800mg/L 350 61.11 825 88.85 1275 89.38 1000mg/L 315 65.00 695 90.61 1000 91.67 1200mg/L 280 68.89 625 91.55 825 93.13 Table 1 showed that the amphiphilic macromolecules of examples 6-10 had good International Application Number: PCT/CN2011/001579 effects for viscosity reduction as to all three oil samples. With the increase of the concentration of the amphiphilic macromolecule solution, the viscosity reduction rate increased. And, when the concentration of the amphiphilic macromolecule solution was the same, the viscosity reduction rate increased with the enhancing of the viscosity of the oil sample. It was believed that the amphiphilic macromolecule could reduce the viscosity of the crude oil remarkably via a synergetic effect between the highly sterically hindered structural unit and the amphiphilic structural unit, which could emulsify and disperse the crude oil effectively.
Industrial Application The amphiphilic macromolecule of this invention can be used in oilfield drilling, well cementing, fracturing, crude oil gathering and transporting, sewage treating, sludge treating and papermaking, and it can be used as intensified oil producing agent and oil displacing agent, heavy oil viscosity reducer, fracturing fluid, clay stabilizer, sewage treating agent, retention aid and drainage aid and strengthening agent for papermaking.
The amphiphilic macromolecule of this invention is especially suitable for crude oil exploitation, for instance, it can be used as an intensified oil displacement polymer and a viscosity reducer for heavy oil. When it is used as an oil displacement agent, it has remarkable viscosifying effect even under the condition of high temperature and high salinity, and can thus enhance the crude oil recovery. When it is used as a viscosity reducer for heavy oil, it can remarkably reduce the viscosity of the heavy oil and decrease the flow resistance thereof in the formation and wellbore by emulsifying and dispersing the heavy oil effectively.
Claims (15)
1. An amphiphilic macromolecule comprising, as repeating units, a structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics, a highly sterically hindered structural unit B and an amphiphilic structural unit C, wherein the highly sterically hindered structural unit B comprises a structure G and a structure of formula (4), wherein the structure G is a cyclic hydrocarbon structure formed on the basis of two adjacent carbon atoms in the main chain, or is selected from a structure of formula (3):
wherein in formula (3), R5 is H or a methyl group; R6 is a radical selected from the group consisting of the structures of formula (5) and formula (6):
in formula (5), a is an integer from 1 to 11, in formula (4), R7 is H; R8 is selected from the group consisting of H, -SO3H
and salts thereof, -(CH2)2CH2C1, -CH2N+(CH3)2(CH2).xi.CH3Cl- and -CH2N+(CH3)2 (CH2)2N+(CH3)2(CH2).sigma.CH3 2Cl-; .xi. and .sigma. are respectively integers from 1 to 15.
wherein in formula (3), R5 is H or a methyl group; R6 is a radical selected from the group consisting of the structures of formula (5) and formula (6):
in formula (5), a is an integer from 1 to 11, in formula (4), R7 is H; R8 is selected from the group consisting of H, -SO3H
and salts thereof, -(CH2)2CH2C1, -CH2N+(CH3)2(CH2).xi.CH3Cl- and -CH2N+(CH3)2 (CH2)2N+(CH3)2(CH2).sigma.CH3 2Cl-; .xi. and .sigma. are respectively integers from 1 to 15.
2. The amphiphilic macromolecule as claimed in Claim 1 wherein R5 is H.
3. The amphiphilic macromolecule as claimed in Claim 1 wherein the structural unit A for adjusting the molecular weight, molecular weight distribution and charge characteristics comprises a (meth)acrylamide monomer unit A1 and/or a (meth)acrylic monomer unit A2.
4. The amphiphilic macromolecule as claimed in Claim 1 wherein the amphiphilic structural unit C has a structure of formula (8):
in formula (8), R9 is H or a methyl group; R10 is -O- or -NH-; R11 is a radical containing a straight-chain hydrocarbyl, a branched hydrocarbyl, a polyoxyethylene (PEO), a polyoxypropylene (PPO), an EO-PO block, a mono-quaternary ammonium salt, a multiple-quaternary ammonium salt, or a sulfonic acid and salts thereof.
in formula (8), R9 is H or a methyl group; R10 is -O- or -NH-; R11 is a radical containing a straight-chain hydrocarbyl, a branched hydrocarbyl, a polyoxyethylene (PEO), a polyoxypropylene (PPO), an EO-PO block, a mono-quaternary ammonium salt, a multiple-quaternary ammonium salt, or a sulfonic acid and salts thereof.
5. The amphiphilic macromolecule as claimed in Claim 3 wherein based on 100 mol% of the entire amphiphilic macromolecule repeating units, the molar percentage of the (meth)acrylamide monomer unit A1 is 70-99mo1%; and the molar percentage of the (meth)acrylic monomer unit A2 is 1-30mol%.
6. The amphiphilic macromolecule as claimed in Claim 1 wherein the molar percentage of the structure G in the entire amphiphilic macromolecule repeating unit is 0.02-2mol%; and the molar percentage of the structure of formula (4) in the entire amphiphilic macromolecule repeating units is 0.05-5mol%.
7. The amphiphilic macromolecule as claimed in Claim 4 wherein based on 100 mol% of the entire amphiphilic macromolecule repeating units, the molar percentage of structure of formula (8) in the entire amphiphilic macromolecule repeating units is 0.05-10mol%.
8. The amphiphilic macromolecule as claimed in Claim 1 wherein the structural unit A for adjusting molecular weight, molecular weight distribution and charge characteristics has a structure of formula (2);
wherein in formula (2), R1 is H or a methyl group; R2 and R3 are independently selected from the group consisting of H and a C1-C3 alkyl group; R4 is selected from the group consisting of H and a methyl group; Gr is -OH or -O-Na+; m and n represent the molar percentage of the structural units in the entire amphiphilic macromolecule, and m is from 70 to 99mol%; n is from 1 to 30mol%.
wherein in formula (2), R1 is H or a methyl group; R2 and R3 are independently selected from the group consisting of H and a C1-C3 alkyl group; R4 is selected from the group consisting of H and a methyl group; Gr is -OH or -O-Na+; m and n represent the molar percentage of the structural units in the entire amphiphilic macromolecule, and m is from 70 to 99mol%; n is from 1 to 30mol%.
9. The amphiphilic macromolecule as claimed in Claim 1 wherein the cyclic hydrocarbon structure formed on the basis of the two adjacent carbon atoms in the main chain is selected from the group consisting of:
10. The amphiphilic macromolecule as claimed in Claim 1, wherein, the highly sterically hindered structural unit B has a structure of formula (7):
in formula (7), the definition on G is as defined in claim 1; the definitions on R7 and R8 are as defined in formula (4); x and y respectively represent the molar percentages of the structural units in the entire amphiphilic macromolecule, and x is from 0.02 to 2mol%, y is from 0.05 to 5mol%.
in formula (7), the definition on G is as defined in claim 1; the definitions on R7 and R8 are as defined in formula (4); x and y respectively represent the molar percentages of the structural units in the entire amphiphilic macromolecule, and x is from 0.02 to 2mol%, y is from 0.05 to 5mol%.
11. The amphiphilic macromolecule as claimed in Claim 4 wherein the structure of R10 and R11 may be selected from -O(CH2)g N+(CH3)2(CH2)h CH3X-, -NH(CH2)i N+(CH3)2(CH2)j CH3X-, -O(CH2)k N+((CH2)p CH3)3X-, -O(CH2)q N+(CH3)2(CH2).alpha.CH(SO3H)CH2(EO).beta.(PO).gamma.(CH2).delta.CH3X-, -NH(CH2)q N+(CH3)2(CH2).alpha.CH(SO3H)CH2(EO).beta.(PO).gamma.(CH2).delta.CH3X-, -O(CH2)q N+(CH3)2(CH2).alpha.CH(COOH)CH2(EO).beta.(PO).gamma.(CH2)CH3X-, -NH(CH2)q N+(CH3)2(CH2).alpha.CH(COOH)CH2(EO).beta.(PO) .gamma.(CH2).delta.CH3X-, -O(CH2)2N+(CH3)2(CH2).epsilon.SO3-, -(OCH(CH2N+(CH3)2(CH2).zeta.CH3Cl-)CH2).eta.O(CH2).theta.CH3, -(OCH(CH2N+((CH2).lambda.CH3)3Cl-)CH2).iota.O(CH2).kappa.CH3, -OCH(CH2N+(CH3)2(CH2)r CH3X-))2, -OCH(CH2N+((CH2)s CH3)3X-))2;
wherein g, i, k and q are respectively integers from 1 to 6; h and j are respectively integers from 3 to 21; p is an integer from 3 to 9; .alpha. is an integer from 1 to 12; .beta.
and .gamma. are respectively integers from 0 to 40; .delta. is an integer from 0 to 21; .epsilon. is an integer from 4 to 18; .zeta. is an integer from 1 to 21; .eta. and .iota. are respectively integers from 1 to 30; .theta. and .kappa. are respectively integers from 3 to 21; .lambda. is an integer from 0 to 9; r is an integer from 3 to 21; s is an integer from 3 to 9; and X- is Cl- or Br-.
wherein g, i, k and q are respectively integers from 1 to 6; h and j are respectively integers from 3 to 21; p is an integer from 3 to 9; .alpha. is an integer from 1 to 12; .beta.
and .gamma. are respectively integers from 0 to 40; .delta. is an integer from 0 to 21; .epsilon. is an integer from 4 to 18; .zeta. is an integer from 1 to 21; .eta. and .iota. are respectively integers from 1 to 30; .theta. and .kappa. are respectively integers from 3 to 21; .lambda. is an integer from 0 to 9; r is an integer from 3 to 21; s is an integer from 3 to 9; and X- is Cl- or Br-.
12. The amphiphilic macromolecule as claimed in Claim 1 wherein the amphiphilic macromolecule has a structure of formula (9):
wherein in formula (9), R4 is selected from the group consisting of H and a methyl group; m and n represent the molar percentages of the structural units in the entire amphiphilic macromolecule, and m is from 70 to 99mol%; n is from 1 to 30mol%;
the definitions on G, R7, R8, x and y are as described in formula (7); R9 is H or a methyl group, R10 is -O- or -NH-; R11 is a radical containing a straight-chain hydrocarbyl, a branched hydrocarbyl, a polyoxyethylene (PEO), a polyoxypropylene (PPO), an EO-PO
block, a mono-quaternary ammonium salt, a multiple-quaternary ammonium salt, or a sulfonic acid and salts thereof; z represents the molar percentage of the structural unit in the entire amphiphilic macromolecule, and z is from 0.05 to 10mol%.
wherein in formula (9), R4 is selected from the group consisting of H and a methyl group; m and n represent the molar percentages of the structural units in the entire amphiphilic macromolecule, and m is from 70 to 99mol%; n is from 1 to 30mol%;
the definitions on G, R7, R8, x and y are as described in formula (7); R9 is H or a methyl group, R10 is -O- or -NH-; R11 is a radical containing a straight-chain hydrocarbyl, a branched hydrocarbyl, a polyoxyethylene (PEO), a polyoxypropylene (PPO), an EO-PO
block, a mono-quaternary ammonium salt, a multiple-quaternary ammonium salt, or a sulfonic acid and salts thereof; z represents the molar percentage of the structural unit in the entire amphiphilic macromolecule, and z is from 0.05 to 10mol%.
13. The amphiphilic macromolecule as claimed in Claim 1, which is a compound of formulas (I)-(X):
m, n, x, y and z in formulae (I) to (X) respectively represent the molar percentages of the structural units in the entire amphiphilic macromolecule, in which, m is from 70 to 99mo1%; n is from 1 to 30mol%; x is from 0.02 to 2mol%, y is from 0.05 to 5mol%, and z is from 0.05 to 10mol%.
m, n, x, y and z in formulae (I) to (X) respectively represent the molar percentages of the structural units in the entire amphiphilic macromolecule, in which, m is from 70 to 99mo1%; n is from 1 to 30mol%; x is from 0.02 to 2mol%, y is from 0.05 to 5mol%, and z is from 0.05 to 10mol%.
14. The amphiphilic macromolecule as claimed in any one of Claims 1 to 13, having a molecular weight of between 1000000-20000000.
15. Use of the amphiphilic macromolecule as claimed in any one of Claims 1 to 14 for oilfield drilling, well cementing, fracturing, crude oil gathering and transporting, sewage treating, sludge treating and papermaking as intensified oil producing agent and oil displacing agent, a heavy oil viscosity reducer, a fracturing fluid, a clay stabilizer, a sewage treating agent, a retention aid and drainage aid and a strengthening agent for papermaking.
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| CN201110210362XA CN102432749B (en) | 2011-07-26 | 2011-07-26 | Amphipol and application thereof |
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| PCT/CN2011/001579 WO2013013357A1 (en) | 2011-07-26 | 2011-09-16 | Amphiphilic macromolecule and use thereof |
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| CN104371061B (en) | 2013-08-14 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of cationic polymer and the application in sealing agent thereof |
| WO2016058960A1 (en) | 2014-10-15 | 2016-04-21 | Snf Sas | Chemically enhanced oil recovery method using viscosity-increasing polymeric compounds |
| RU2700418C2 (en) * | 2017-07-11 | 2019-09-17 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ярославский государственный технический университет" ФГБОУВО "ЯГТУ" | Method of producing amphiphilic random copolymers |
| CN109992836B (en) * | 2019-03-05 | 2021-09-28 | 中国石油化工股份有限公司 | Efficient selection method of viscoelastic particle oil displacement agent suitable for different oil reservoir requirements |
| US11274240B2 (en) | 2019-07-10 | 2022-03-15 | Halliburton Energy Services, Inc. | Cationic formation stabilizers compatible with anionic friction reducing polymers |
| CN110511329A (en) * | 2019-07-18 | 2019-11-29 | 中国石油天然气股份有限公司 | Aromatic group-containing polymer surfactant and preparation method and application thereof |
| CN112358862B (en) * | 2020-09-07 | 2022-08-09 | 中国石油天然气股份有限公司 | Oil displacement and viscosity reduction fracturing fluid suitable for low-fluidity compact oil reservoir |
| CN114426832A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Water-control viscosity reduction method of water-control viscosity reducer for bottom-water heavy oil reservoir |
| CN114456793B (en) * | 2020-10-21 | 2023-06-20 | 中国石油化工股份有限公司 | Self-viscosity-reduction fracturing fluid for low-permeability heavy oil reservoir and preparation method thereof |
| CN114276488B (en) * | 2022-03-03 | 2022-06-03 | 河南博源新材料有限公司 | Long-chain branch multi-head cationic polyacrylamide and application thereof |
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| US4653584A (en) * | 1985-05-30 | 1987-03-31 | The Standard Oil Company | Maleimide-modified bioresistant polymers and enhanced oil recovery method employing same |
| US4959432A (en) | 1986-05-19 | 1990-09-25 | Union Carbide Chemicals And Plastics Company Inc. | Acid viscosifier compositions |
| CN1314720C (en) * | 2004-12-13 | 2007-05-09 | 大连广汇化学有限公司 | Preparation method of high molecular weight amphoteric high molecule |
| FR2914647B1 (en) * | 2007-04-05 | 2011-10-21 | Rhodia Recherches Et Tech | COPOLYMER COMPRISING BETAINIC UNITS AND HYDROPHOBIC AND / OR AMPHIPHILIC UNITS, PREPARATION METHOD, AND USES. |
| CN101284893B (en) * | 2008-06-06 | 2010-10-27 | 成都理工大学 | Comb-typed amphiphilic water-soluble co-polymer, method for preparing same and use |
| CN101463116B (en) | 2009-01-12 | 2011-07-20 | 成都理工大学 | Non-linear associating water-soluble quadripolymer, and preparation and use thereof |
| CN101492515B (en) * | 2009-01-23 | 2011-06-15 | 成都理工大学 | Acrylic amide modified graft copolymer, preparation method and application thereof |
| CN101857663B (en) | 2009-04-09 | 2012-04-25 | 北京佛瑞克技术发展有限公司 | Method for preparing acid fracturing, temperature-controlled and variable-viscosity polymer and polymer cross-linked body |
| CN101570697B (en) * | 2009-06-01 | 2013-01-02 | 中国科学院化学研究所 | Crude oil emulsion splitter |
| CN101781386B (en) * | 2009-12-31 | 2012-06-13 | 中国科学院化学研究所 | Method for preparing amphiphilic macromolecule oil-displacing agent |
| CN101798503B (en) * | 2010-01-05 | 2012-07-11 | 西南石油大学 | Novel polymeric oil-displacing agent for improving recovery ratio and application thereof |
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